Oxime ethers and pesticidal preparations containing them

ABSTRACT

NEW OXIME ETHERS AND PESTICIDAL AND HERBICIDAL PREPARATIONS CONTAINING THEM ARE DISCLOSED. THE OXIME ETHERS CORRESPOND TO THE FORMULA   (2-R5,3-R4,4-R3,6-(O2N-)PHENYL)-O-N=C(-R1)-R2   WHEREIN R1 IS A HYDROGEN ATOM OR A LOWER ALKYL RADICAL, R2 IS ALIPHATIC, CYCLOALIPHATIC, ARALIPHATIC, AROMATIC OR HETEROCYCLIC RADICAL, OR WHEREIN R1 AND R2 FORM PART OF A SATURATED OR UNSATURATED CARBOCYCLE OR A 5-, 6- OR 7MEMBERED HETEROCYCLE, R3 IS A NITRO, TRIFLUOROMETHYL, FORMYL, LOWER CARBALKOXY, SULFAMYL OR MONO- OR DILOWER ALKYSULFAMY RADICAL, R4 AND R5 EACH IS A HYDROGEN OR HALOGEN ATOM, AN AMINO, MONO- OR DI-LOWER ALKYLAMINO, LOWER ALKOXY, CYCLOALKOXY, LOWER ALKYLTHIO, NITRO, LOWER CARBALKOXY, ARYLTHIO, LOWER ARALKYLTHIO GROUP OR 5-, 6- OR 7-MEMBERED HETEROCYCLE.

United States Patent 3,733,359 OXIME ETHERS AND PESTECIDAL PREPARA- TIONS CONTAINING THEM Adolf Hubele, Riehen, Switzerland, assignor to Ciba- Geigy AG, Basel, Switzerland No Drawing. Continuation-impart of application Ser. No. 521,413, Jan. 18, 1966. This application June 16, 1970, Ser. No. 46,832 Claims priority, application Switzerland, Jan. 22, 1965, 915/65; July 9, 1965, 9,630/65 Int. Cl. C07c 131/00 US. Cl. 260-566 AE 3 Claims ABSTRACT OF THE DISCLOSURE New oxime ethers and pesticidal and herbicidal preparations containing them are disclosed. The oxime ethers correspond to the formula CROSS REFERENCE This is a continuation-in-part of application Ser. No. 521,413 filed Jan. 18, 1966 now abandoned.

BACKGROUND OF THE INVENTION The present invention provides new oxime ethers and pesticidal preparations containing them. The oxime ethers correspond to the formula wherein R is a hydrogen atom or a lower alkyl radical; R is an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radical; or wherein R and R form part of a saturated or unsaturated carbocycle or a 6- or 7-membered heterocycle; R is a nitro, trifluoromethyl, formyl, lower carbalkoxy, sulfamyl or monoor dilower alkylsulfamyl radical; R and R each is a hydrogen or halogen atom, an amino, monoor di-lower alkylamino, lower alkoxy, cycloalkoxy, lower alkylthio, nitro, lower carbalkoxy, arylthio, lower aralkylthio group or 5-, 6- or 7-membered heterocycle.

R in the above formula stands for a lower alkyl radical. Such radicals contain 1 to 4 carbon atoms and may be branched or unbranched such as the methyl and ethyl groups or the normal or iso-propyl or butyl group or secondary or tertiary butyl group. Preferred groups, however, are besides the hydrogen atom the methyl and ethyl radicals.

R stands for an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radical. The aliphatic radical may be branched or unbranched, saturated or unsaturated. Preferably such radicals contain up to 8 carbon atoms Patented May 15, 1973 ice and are alkyl or alkenyl radicals which may be substituted or unsubstituted. Suitable substituents are for instance halogen atoms, such as fluorine, chlorine or bromine or hydroxy or alkoxy groups. The cycloaliphatic radicals contain 3 to 8 carbon atoms and may be saturated or unsaturated and monoor polycyclic. As a rule they contain 3 to 12 carbon atoms and are saturated. They preferably are monoor bicyclic and have 3 to 7 ring members. The araliphatic radicals contain in the aromatic moiety at least one benzene nucleus and in the aliphatic moiety preferably an unbranched chain containing 1 to 4 carbon atoms. This aliphatic chain may be saturated or unsaturated, substituted or unsubstituted. Suitable substituents are hydroxy groups and halogen atoms, such as chlorine and especially bromine. Suitable chains contain 2 carbon atoms and are saturated; they may also contain one or two bromine atoms or one double bond. Aromatic radicals are to be understood as being substituted or unsubstituted phenyl radicals or condensed ring systems. The preferred embodiments are substituted and unsubstituted phenyl radicals. Suitable substituents on the phenyl moiety are e.g. halogen atoms such as fluorine and especially chlorine, bromine and iodine; lower alkyl and alkoxy groups containing 1 to 4 carbon atoms; hydroxy groups; amino groups which may be substituted by one or two lower alkyl, lower alkoxyalkyl or lower alkanol radicals; nitro groups; lower alkyl carbamoyl radicals; phenoxy groups which may be substituted by one or more of the substituents enumerated above for the phenyl radical especially by nitro groups. The heterocyclic radicals coming into consideration particularly are 5- or 6 membered and contain at least one oxygen or sulfur especially however nitrogen atom. These heterocycles may be substituted, preferably by lower alkyl radicals, especially the methyl group. Examples of such heterocycles are i.a. pyridine and quinaldine compounds.

R stands for a trifiuoromethyl, formyl, nitro, lower carbalkoxy, sulfamyl or monoor di-lower alkylsulfamyl group. The alkyl moieties of the carbalkoxy and alkylsulfamyl group contain 1 to 4 carbon atoms and may be branched or unbranched. Preferred alkyl moieties contain 1 or 2 carbon atoms. However, suitable substitutents are not limited to the above enumeration. Thus also halogenalkyl groups quite generally may be used. Moreover, halogen atoms such as chlorine, bromine and iodine; alkyl groups containing 1 to 6 carbon atoms, the carboxyl group; lower alkylor ary1-, especially phenylcarbamyl groups; the sulfonic acid groups; and lower alkylsulfonyl groups may be used likewise.

R and R each stands for a hydrogen or halogen atom, a lower alkyl, amino, monoor di-lower alkylamino, lower alkoxy, cycloalkoxy, lower alkylthio, lower carbalkoxy, arylthio, lower aralkylthio, nitro or heterocyclic radical. The halogen atoms may be elected from fluorine, bromine, iodine and especially chlorine. The lower alkyl moieties enumerated above contain 1 to 4 carbon atoms and may be branched or unbranched. The heterocyclic radicals are 5-, 6- or 7-membered, especially 5- or 6- membered, and contain as hetero-atoms one or more oxygen, sulfur or especially nitrogen atoms. Such heterocyclic radicals are i.a. the pyridino and morpholino radical. The cycloalkoxy radicals are 3 to S-membered, especially however G-membered. Representative of such radicals is the cyclohexoxy radical. Especially suitable oxime ethers are those which correspond to the formulae /C=NO Ra 2 R (III) wherein R R R R and R have the meanings given above. More particularly R stands for a nitro, trifluoromethyl, formyl, methylcarbonyl, methylsulfamyl or a dimethylsulfamyl radical, R for a hydrogen or chlorine atom, an amino, methyl amino, dimethyl amino, isopropylamino, methoxy, ethoxy, benzylmercapto or morpholino group, and R for a hydrogen atom, a methyl, sec.butyl, carbomethoxy, nitro or cyclohexoxy radical.

From among the compounds of Formula III those should be specially mentioned which correspond to the formulae wherein R and R have the meanings given above and R and R each is hydrogen, lower alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.butyl, tert. butyl amyl or cycloalkyl, such as cyclopentyl or cyclohexyl.

From among the compounds of Formulae H and III those are preferred which correspond to the formula wherein R and R have the above meanings. More particularly R may stand for hydrogen and R for a substituted phenyl radical. Such compounds correspond to the formulae wherein R R and R have the meanings given above and X and X each stands for halogen. More specifically X represents chlorine bromine and iodine, whereas X stands for chlorine.

The oxime ethers of the Formulae I to VI may be derived from aliphatic, araliphatic, aromatic or heterocyclic aldehydes or ketones, and also from quinones and endocyclic ketones for example fluorenone, indanone, acenaphthenone, anthrone, N-methylpyridone, N-methylpiperidone, furfurol or nitrofurfurol.

Preferred use is made of oxime ethers derived from aliphatic aldehydes or ketones, from araliphatic aldehydes or ketones, or from aromatic or heterocyclic aldehydes or ketones.

Suitable aliphatic aldehydes are simply constituted aldehydes for example acetaldehyde, propionaldehyde, butyraldehyde or aldehydes having a longer chain, for example heptaldehyde, stearaldehyde or unsaturated aldehydes for example 'crotonaldehyde. Suitable aliphatic ketones are simple ketones for example acetone, methylethyl ketone, hexanone-(3), diisopropylketone, mesityl oxide, and phorone. Suitable araliphatic or aromatic aldehydes and ketones are cinnamic aldehyde, hydrocinnamic aldehyde, halogen adducts or cinnamic aldehyde for example dibromo-cinnamic aldehyde, diiodo-cinnamic aldehyde, acetophenone, propiophenone, benzaldehyde, nuclear halogenated, alkylated, nitrated and alkoxylated benzaldehydes. Examples of suitable cyclic ketones are cyclopentanone, cyclohexanone, cycloheptanone as well as their cyano derivatives. Suitable heterocyclic ketones and aldehydes are, for example, picoline aldehyde, nicotine aldehyde, isonicotine aldehyde and N-alkylpiperidones.

If such aldehydes or ketones contain aromatic radicals, their suitably substituted derivatives may likewise be used. These substituents may be of a non-functional kind, for example halogen atoms, nitro or nitroso groups, or of a functional kind or derived from functional substituents, being, for example hydroxyl, acyloxy, carbamoyloxy, alkoxy, aryloxy, thiol, acylthio, alkylthio, trifiuoromethyl, cyano, formyl, amino, alkylamino, dialkylamino, arylamino, diarylamino, carboxy or carbalkoxy groups.

By virtue of their broad biocidal spectrum the new oxime ethers offer the special advantage that they are suitable for combating a very wide variety of vegetable and animal pests. They are suitable not only for use as herbicides, which is the preferred utility, but when used in a concentration that does not produce any phytotoxic effects, they are very useful in plant protection for combating harmful micro-organisms, such as phytopathogenic fungi, for example Alternaria solam', Phytophthora infestans and Septoria apii, and act also against harmful insects, acarides, nematodes and their ova and larvae. They may also be used quite generally as microbicides, for example against Aspergillus species, and as insecticides, for example against midges and flies.

The oxime ethers according to this invention may be used per se or in admixture with suitable carriers. Such carriers may be solid or liquid. The pesticidal preparations thus formed may therefore contain a solid carrier, a solvent diluent, dispersant, wetting agent, adhesive, fertilizer and/or other known pesticides.

For the manufacture of solutions of compounds of the general Formula I for direct spraying there may be used, for example, petroleum fractions of a high to medium boiling range, for example diesel oil or kerosene, coal tar oil and oils of a vegetable or animal origin, as well as hydrocarbons for example alkylated naphthalenes, tetrahydronaphthalene if desired in conjunction or admixture X (VI a with xylene mixtures, cyclohexanols, ketones, chlorinated hydrocarbons for example trichloroethane or tetrachloroethane, trichloroethylene, trior tetrachlorobenzene. It is advantageous to use organic solvents boiling above 100 C.

Aqueous forms of applications are prepared most advantageously from emulsion concentrates, pastes or wettable spray powders by addition of water. Suitable emulsifying or dispersing agents are non-ionic products, for example condensation products of aliphatic alcohols, amines or carboxylic acids containing a long-chain hydrocarbon residue of about 10 to 20 carbon atoms with ethylene oxide, for example the condensation product of octadecyl alcohol with 25 to 30 mols of ethylene oxide, or of soybean fatty acid with 30 mols of ethylene oxide, or of commercial oleylamine with 15 mols of ethylene oxide, or of dodecylmercaptan with 12 mols of ethylene oxide. From among suitable anionic emulsifiers, there may be mentioned the sodium salt of dodecyl alcohol sulphuric acid ester, the sodium salt of dodecylbenzenesulphonic acid, the potassium or triethanolamine salt of oleic or abietic acid or of mixtures of these acids, or the sodium salt of a petroleumsulphonic acid. Suitable cationic dispersants are quaternary ammonium compounds, for example cetyl pyridinium bromide or dihydroxyethyl benzyl dodecyl ammonium chloride.

For the manufacture of dusting and casting preparations, there may be used as solid vehicles talcum, kaolin, bentonite, calcium carbonate, calcium phosphate, or coal, cork meal, wood meal or other materials of vegetable origin. It is also very advantageous to manufacture preparations in granular form. The various forms of application may contain the usual additives for improving the distribution, the adhesion, the stability towards rain or the penetration; as such substances there may be mentioned fatty acids, resin, glue, casein and alginates. The preparations of this invention may be used by themselves ,or in conjunction or admixture with conventional pesticides, especially insecticides, acaricides, nematocides, bactericides or further fungicides or herbicides.

Especially potent herbicides are those preparations which contain as active ingredient a compound of the formula wherein R represents :a hydrogen atom or an aliphatic radical and R an aliphatic radical or an unsubstituted or substituted phenyl group, A represents NO CHO, COOH or C alkyl, and B stands for hydrogen, NO COOH, COO alkyl or chlorine. The phenyl radical R may carry various substituents, for example halogen atoms, nitro, alkyl, hydroxyl or alkoxy groups and/ or carbamoyloxy groups.

Particularly potent herbicides are the compounds of the Formula Ia wherein R and R have the following meanings:

H OHa-HN-COOQ- OCHa Especially useful acaricides are those preparations which contain as active ingredient a compound of the formula R (IVa) wherein R represents a hydrogen atom and R a phenyl radical which may be substituted by halogen atoms or alkyl or alkoxy groups, or wherein R and R represent alkyl radicals or are part of an isocyclic residue.

Especially potent are the compounds of the formula CHaO CzHaO OOH;

C53 0113- CH- The active ingredients of Formula I may be manufactured according to known methods, such as e.g.:

A salt of a ketoxime or aldoxime of the formula wherein R and R have the above meanings and Me stands for a metal atom, preferably an alkali metal atom, is reacted with a halogeno-benzene of the formula Hal- R 3 wherein R to R have the above meanings and Hal represents a fluorine, chlorine, bromine or iodine atom.

The reaction may be carried out in a solvent, for example in ethanol, methanol, acetonitrile or dioxan, as a rule at room temperature; in many cases it is accompanied by a spontaneous rise in temperature. The oxime ethers obtained in this manner are very easy to isolate by diluting the reaction solution with water. The ethers precipitate and may, if desired, be recrystallized. This process may be varied in that following upon the formation of the oxime ether one or several groups, R R R R are subsequently converted.

More especially, halogen atoms R and/or R may be exchanged for compounds containing active hydrogen atoms, thus for example for ammonia, primary or secondary aliphatic, araliphatic or aromatic amines, alcohols, phenols, alkanethiols or thiophenols.

The oxime ethers accessible in this manner may take the syn-form or the anti-form. As a rule, they are obtained in the form of a mixture of isomers, which can be resolved into the two forms by a usual operation, for example crystallization or adsorption. For the manufacture of the preparations of this invention, it sufiices to use the mixture of isomers as obtained by the reaction.

The present invention further includes new oxime ethers of the general formula wherein R and R have the above meanings and R represents a trifiuoromethyl, formyl, unsubstituted or substituted carboxyl or possibly alkylated sulphamyl residue, and R represents a hydrogen atom or a nitro group, or wherein R stands for the nitro group and R for a possibly esterified carboxyl group.

The following examples illustrate the invention:

EXAMPLE 1 EXAMPLE 2 CH3 N09 A seolution of sodium ethylate prepared from 13.1 parts of sodium and 300 parts by volume of absolute ethanol is added drop by drop during 30 minutes, at room temperature, to a solution of 82 parts of ortho-methoxybenzaldehydeoxime and 115 parts of 4-chloro-1,3-dinitrobenzene in 1000 parts by volume of acetonitrile. After 4 hours, the batch is diluted with 3000 parts by volume of water, filtered and recrystallized from toluene+acetone. The product melts at 184-184.5 C.

EXAMPLE 3 A solution of sodium ethylate prepared from 18.5 parts of sodium and 500 parts by volume of absolute ethanol is added drop by drop during 30 minutes at room temperature to a solution of 90 parts of cyclohexanone oxime and 162 parts of 4-chloro-1,3-dinitrobenzene in 500 parts by volume of acetonitrile. After 4 hours, the batch is diluted with water filtered and recrystallized from acetonitrile. The product melts at 1055-106 C.

EXAMPLE 4 A solution of sodium ethylate prepared from 12 parts of sodium and 250 parts by volume of absolute ethanol is added drop by drop at room temperature to a solution of 50.5 parts of methyl-isopropyl ketonoxime and 101.3 parts of 4-chloro-1,3-dinitrobenzene in 400 parts by volume of acetonitrile, while stirring. After 12 hours, the batch is diluted with water, filtered and recrystallized from acetonitrile. The product melts at 85 to 86 C.

EXAMPLE 5 EXAMPLE 6 An oxime salt solution of 43.5 parts of isobutyraldoxime and 10.5 parts of sodium in 300 parts by volume of absolute ethanol is added drop by drop during 30 minutes at 5 C. to a mixture of 93 parts of 4-fiuoro- 1,3-dinitrobenzene and 200 parts by volume of acetonitrile, while stirring. The batch is then stirred for 3 hours at room temperature, diluted with ice water, filtered and recrystallized from acetonitrile. The product melts at to 83 C.

EMMPLE 7 A solution of 54 parts of the cyclohexanone oxime sodium salt in 800 parts by volume of dioxane is added drop by drop at room temperature during 30 minutes to a mixture of 106 parts of 4-chloro-3nitrobenzenesulphonic acid-(l)-dimethylamide in 500 parts by volume of dioxan while stirring. During the addition, the temperature rises to 35 C. After 2 hours, the batch is heated for /2 hour at 50 C., then diluted with ice water, filtered, and recrystallized from ethanol. The product melts at 124 to 125 C.

33 parts of a-methylaminopropionitrile in 200 parts by volume of dioxan are added drop by drop within 1 hour at 50 C. While stirring to 69 parts of couminaldehyde oxirne-O-(5-chloro-2,4-dinitro-phenyl ether) in 700 parts by volume of dioxan, during which the temperature of the solution rises slightly.

After 1 hour, the batch is diluted with ice water, filtered and recrystallized from ethanol+dimethy1formamide. The product melts at 161 to 162 C.

EXAMPLE CH3 3 mm.

23 parts of isopropylamine in 100 parts of dioxan are added drop by drop during 1 hour, at 50 C., to 77 parts of fiuorenone oxime O (5 chloroQA-dinitrophenyl ether) in 1500 parts by volume of dioxan. The batch is then refluxed for 3 hours at 80 C., another parts of isopropylamine are added and the mixture is heated for 3 hours at 80 C., diluted with ice water, filtered and digested with hot dimethylformamide. The product melts at 240 to 241 C. with decomposition.

EXAMPLE 11 An oxime salt solution prepared from 86 parts of 3,4- dichlorobenzaldoxime, 10.3 parts of sodium and 600 parts by volume of absolute ethanol is added drop by drop at room temperature within V2 hour to 130 parts of isopropyl (5 chloro 2,4-dim'trophenyl)-sulphide in 400 parts by volume of acetonitrile, while stirring. After 3 hours, the batch is diluted with ice water, filtered and recrystallized from acetonitrile. The product melts at 191 to 192 C.

10 EXAMPLE 12 (12) 0 CH N01 /C=NO -N0a R2 TABLE 1 0: Melting Compound No; R; point, C.

C1- CH:

(CH3) zN -CH= 17- T.':.'*:.":::.*.'..".' 1| IO 2 189-190. 5

onmn-o-o-Qon:

HO- CH:

2U--.:..' Cl 199. 5-200 23. (I) CH3 202-203 TABLE 1Cont1nued TABLE 1Oontinued 1 R1 Melting Meltin Compound No. R2 point, C. Compound No. Rz point, C

0112- Cg: /CHz /C= 25 200. -207 0 I 2 (I111; 107-100 CHz-C 0H1 mom a:

27 0E3 71-71.5 0 CH1 C: 43 I 133-100 CH I 23 141-142 (C2H5)1N OH: I I

29 OCH; 1435-144 30 I 44 (CHmCIl-Cga 75-77 Como-@011:

(CH3)2CHCHg 30 ..z.. 0 CH3 175-175. 5

45 /CH:CH: 81-83 CH3O- (3H, 0 31 CH3 105-190 E CH2 CH2 16 C2115 91-92 32 ll-I3 130-131 CzHi GHE (CHQ)S C= CHzC|7-CH2C= 34 CH3 1035-100 Q 4s 211; CH; 3031 1 GHQ-0114311143: 49 (3H c m 50-53 35 CH 1 2 0-2 CH;CH(CH2);C=

8 5o =177-17s 01- C= N --0H:

36 C 11 39-39, 5 51 CH: 161-163 I CHC= CH3(CH2)5C= 5.; CH3 135.142 30 CH3 cm 35-97 CH=CH$= CCH2 6 0 55 CH3 2 183-184 a E QCHBr-CHBr-:

See footnotes at end of table.

TABLE 2Contin11ed TABLE L Cntinued 0: C: Melting Melting Compound No. R; point, C. Compound N0. R2 point, C.

94 (3H3 68-69 I I CZH5C= 95 02115 N C2H5C= 86 (1H3 CH3 96 Cg: 143-144 om-cn-om-: o11-o11= s7 0113 186-187 011;

15 Q-CHBr-CHBr-(E: 96a 11 2 175-170 38 214-215 HOCH= 90b 1|3r 2 131-132 g HOGH= 1 88a 01 104-190 Br HO- CH= 96c 1 7 185-186 01 HO-Q-CH: 88b Br 137-139 I HOCH= K Brown oil.

2 Decomposition. The following oxime ethers of 2,4-dinitro-6-carbome- 88c I 1176478 thoxyphenol were prepared in a similar manner:

I C=NO -NO;

40 1 Decomposition. OOOH; 1 Brown oil.

TABLE 4 R1 The following oxime ethers of 2 n1tro-3-carbome- \C thoxyphenol were prepared by methods analogous to Melting those described in the foregoing examples: Compound No. R2 point,C.

C=N=O COOCH3 98 5 5 R1 TABLE 3 99 Cl 105-107 Me1ting Compound No. R? po1nt,C.

89 68-69 100 (31 122-124 9o (r011 135-137 Q -1 r 101-... 30113 133 35 91 134-130 05 Q CH:

c1 -CH= Cl CH3- y l 92 c1 -c11= 109-171 103 0 4 CH OH 1 HO CH: 10 (g a a See footnote at end of table.

TABLE 4--'Continued TABLE 5-Co11tinued Melting Compound No. R: P 5 Compound No. 112 poifi z 105 CH: 1 1-1 3 118 0H CH;

119...--.:.':.";.:.: ceHu Cam-J1:

1 Brown 011.

2 Furthermore, the following oxime ethers of 2-nitro-4- formylphenol were prepared analogously:

R N on l /C=N-O CHO 109 N01 156-167 RI CH: TABLE 6 (maom),- Melting 111 (1) Compound No. R: point, C.

oH,-oH- c11, ,o= 121 I 197-198 112 a) HOQCH:

C H O= 113.. (3H 141-143 1 -CH=CH -O= 122-...13355: c1 QCH: 143-144 114 .4 H: 2 7 7 Br 190491 CjHPH-CH Br 165-167 HO OH:

I 110-- CH:

1 Decomposition.

B I Furthermore, the followmg ox1me ethers of 2-nitro-4-tri- Bmwn fluoromethylphenol were prepared analogously: The following oxime ethers of 2,4-dinitro-6-carboxyclom hexoxyphenol were prepared m a simllar manner.

NO R1 2 5 TABLE 7 5 \C=NO NO: R!\ R, 0-.-

Melting Compound No. B? point, C.

123 CHaO 143-144 TABLE 5 R1 CgHsO C Moligg 124 cm 83-85 Compound No. R1 P 20- 13; 7);

1 CH; ,/CH: C:

CH-G

CH: CH!

122-123 maus 149-151 WQCE 111-113 See footnote at end or table.

TABLE 7Contlnued TABLE 8Contlnued C: C: Melting Melting Compound No. R; point, 0. Compound No. R; point, C. 1241) I 1 182-183 1335 c1 1 181-185 110- CH: 110- CH:

1 Decomposition.

The 2,6-dinitro-4-trifluoromethylphenyl ether of the acetonoxime (compound No. 125) melts at 80-8l C.

Furthermore, the following oxime ethers of 2,4,6-trinitrophenol were manufactured analogously:

/C=NO NO: RI

C: Melting Compound No. R; point, C.

The following oxime ethers of 2-nitro-4N,N-dimethylsulphamylphenol were manufactured analogously:

o N OQ-SOMGH :1

1 Decomposition.

The cyclohexanone oxime 2 nitro-4-N-methylsulphamylphenyl ether (compound 134) melts at 129-130" 15 C.

Furthermore, the following oxirne ethers of 2,4-dinitro-5-aminophenol were manufactured analogously:

The following oxime ethers of 2,4-dinitro-5-isopropy1- aminophenol were manufactured analogously:

/C=N0 N 0: R:

NHCaHKi) TABLE 10 C: Melting Compound No. R: point, C.

=CH CH; C:

CCH| CH CH;

The followin g oxime ethers were also manufactured in an analogous way to that described above,

Tum-Continued Melting Compound No. Formula point, C.

155 NO: Oil

CH3 C2 5 C:H5CHCHzC=N-O -NO:

(EHOHICHI CH:

156 lilo: 4 -50 (fHCHgCH; CH

157...'....:....:...: CHz-CH: NO: Oil

| C=NO Ng CE:

CH:CH| HOHzCH N09 NO-NO:

(fHCHzCHg CH 159 .:...r.r:.- NO: 58-59 CH CH3 CHaCH-C=N--O -N02 CH: C2115 CzH5C-CHzC=N-0 N0:

HCHQCH] F OzN-C=N0- NO:

([lHCHaCHz CH:

162 ill N02 1 136-137 HOCH=NO NO: I (|JHCH:CH3

1 Decomposition.

EXAMPLE 13 nate, 45 g. of dicresyl methanedisulphonic acid, g. of a (a) A mixture of 50 g. of the active ingredient No. 14, g. of Hisil (a silica preparation), g. of kaolin, 3.5 g. of flotation agent (for example a condensation product of 1 mol of para-octylphenol with 6 to 10 mols of ethylene oxide) and 1.5 g. of a wetting agent (for example the sodium salt of 1-benzyl-2-heptadecylbenzimidazole-disulphonic acid) is finely ground to form a wettable powder containing of the active product.

The active ingredient No. 21 is formulated in a similar manner, except that 25 g. of chalk are used instead of 25 g. of kaolin. In an identical manner, the active substance No. 14 of Example 4 is formulated.

(b) 500 grams each of the active ingredients Nos. 5

mixture of 40% of an alkylarylpolyether alcohol and 60% of magnesium carbonate, and 335 g. of kaolin. In each case, the resulting mixture may be diluted with water to form a stable emulsion.

EXAMPLE 14 and 67 are mixed with 110 g. of ammonium ligninsulphogenuine leaves.

The following results were recorded:

Compound Number Species of plant 1 2 13 14 15 17 18 19 21 26 27 29 32 33 36 37 41 43 46 Beta vulguris 9 9 9 9 9 10 10 9 10 10 10 10 9 8 10 10 10 10 10 Calendula. 9 10 10 10 10 10 10 10 8 10 10 9 8 7 10 9 10 10 10 inum 10 8 8 10 10 10 10 10 8 10 10 10 10 7 10 10 10 8 9 Brasslca 9 10 10 10 9 10 10 9 10 10 1O 10 10 8 10 10 10 10 10 Daucus 9 10 10 9 2 8 10 10 8 9 8 2 10 6 10 9 9 8 8 Laotuca 10 10 10 10 2 5 10 10 10 10 10 2 8 5 10 9 10 10 10 Me dicago 2 4 4 10 6 10 10 9 10 10 10 10 2 2 2 3 6 10 10 oya 1 2 9 10 1 4 8 7 8 4 1 1 0 0 0 0 8 1 Tritioum. 0 0 0 1 0 0 0 0 0 1 1 1 0 0 0 0 0 0 1 Hordeum 2 1 2 0 2 3 3 2 1 3 2 1 2 1 1 1 0 0 1 Sorghum 1 1 0 1 1 2 4 1 2 2 1 1 1 1 2 2 1 0 0 Phaseolus--- 4 9 4 2 6 5 9 7 4 5 1 4 7 8 4 5 8 4 Compound Number 10 10 10 10 10 10 8 8 10 8 10 10 10 10 8 10 8 10 8 10 10 10 10 10 8 10 10 10 10 10 10 8 7 8 10 9 7 10 10 10 10 10 8 10 8 10 10 10 10 8 8 10 10 10 10 10 10 10 8 10 10 10 8 8 10 10 8 8 10 8 6 10 8 8 e 6 10 10 9 5 10 8 10 8 s 8 10 10 10 10 9 8 8 8 10 10 9 10 8 5 1O 8 1O 10 9 10 10 10 6 8 9 10 8 10 6 10 10 10 1O 8 10 10 10 8 8 1 6 1 1 1 1 1 5 8 10 8 1 1 8 8 2 10 10 0 0 0 1 0 0 1 0 1 0 1 1 1 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 1 0 1 1 1 1 1 1 0 0 1 2 2 1 0 1 0 1 0 1 0 0 0 1 1 2 4 1 4 8 6 7 5 4 7 8 8 5 10 10 6 4 5 Note.0=No efiect; 5=Damage that spreads; 5=Damage that results in the plant dying oft; 10=P1ant completely destroyed.

Each of the active compounds Nos. 5, 10, 20, 56, 67, 88 and 99, formulated as described in Example 13b was sprayed on the soil in an amount of 0.5 kg. per hectare, in a greenhouse test immediately after sowing-Le. by

the preemergence method. The test plants and the results achieved are listed in the following table:

Compound Number Species of plant 5 10 56 67 88 99 Tritlcum 2 2 2 2 2 1 1 Hordeu.m 2 2 1 1 2 2 1 Avena" 10 s s s s 10 8 Poem 10 10 10 1o 10 1o 8 Dacty 10 10 10 1o 10 1o 10 Linum 3 3 5 5 3 5 10 Brassic 3 3 2 2 1 0 0 Laetuca. 1o 8 s 10 10 10 10 Medieago 4 5 s 8 s 10 s oya 1 1 1 1 1 o 0 Phaseolus 1 1 o 1 0 1 0 NOTE.0=N0 efiect; 10=Plant completely destroyed.

When applied in an amount of 0.5 kg. of active compound only a few plants were strongly affected, above all Avena, Poa, Dactylis and Lactuca, whereas the others were not damaged at all or only to a very small extent, such as Triticum, Hordeum, Brassica, Soya and Phaseolus. (b) The active substances Nos. 5 and 67, formulated as described in Example 13b, in an amount of 4.0, 2.0, 1.0 and 0.5 kg. of active substance per hectare, were sprayed over the soil in a greenhouse test immediately after seeding, that is to say, by the pre-emergence method. The seedlings treated and the results achieved are shown in the following table:

Active substance No. 5 Active substance No. 67

Kg. AS 4. 2 1 0.5 4 2 1 0.5

10 9 2 10 7 7 2 5 5 2 10 4 a 2 10 10 10 10 1o 10 s 10 10 10 10 10 10 10 1o 10 10 10 10 10 10 1o 10 3 10 a s a 10 a 3 1o 4 2 1 1o 10 10 10 10 10 10 1o 10 4 10 10 1o 8 y 7 4 1 9 4 2 1 Phaseolus 5 1 1 1 4 1 0 o NOTE.0=N0 effect; 10=Plant completely destroyed.

When applied in an amount of 4.0 kg. per hectare both these products of the invention displayed a broad efiect, whereas with 0.5 kg. of active substance only some plants were strongly effected, above all Avena, Poa, Dactylis and Lactuca, whereas others were not damaged at allor only very little, for example Triticum, Hordeum, Brassica, Soya and Phaseolus.

Accordingly, the two new active substances may be used as total herbicides by the pre-emergence method or, when used in a suitable concentration, for the selective control of weeds, for example in grain crops (Triticum and Hordeum), varities of cabbage (Brassica) and leguminoses (soybeans and phaseolus beans).

EXAMPLE 15 Mixtures containing 50 g. of the active substances Nos. 16, 20, 22, 4 and 66 each, 3.5 g. of a non-ionic, and 1.5 g. of an anionic wetting and dispersing agent are finely ground with 50 g. of a vehicle. The wettable spray powders thus obtained may be diluted with water in any desired proportion.

EXAMPLE 16 10 to 40 grams of each of the compounds 68, 73, 75, 98, 76 and 94 are made up with an adequate amount of an emulsifier (sulphonate-nonionic mixture) in xylene to a volume of 100 ml. These emulsion concentrates may be diluted with water to the desired concentration and used as fungicides.

EXAMPLE 17 The products of this invention, for example compound No. 16, are also distinguished by their action against genuine powdery mildew. Zucchetti plants (Cucumis pepo) were trained in a greenhouse and once sprayed prophylactically with a broth containing as active ingredient 0.2% of the preparation formulated as described in Example 15. 2 days after having been sprayed, the plants were infested with spores of Erysiphe cichoracearum and 12 to 14 days later checked for fungus attack. Compared with the untreated control (efiect: nil) the sprayed plants displayed a efiect without having developed phytotoxic damage.

Effects similar to those against Erysiphe cicoracearum described above were observed with the following compounds, which were readily tolerated by the Zucchetti plants:

Compound No.: Effect in percent EXAMPLE 18 The action of the compounds of this invention against leaf spot fungi was confirmed on celery (Apium graveolens) with the fungus Septoria apii. Celery plants were trained in a greenhouse and, 2 days before infection with the fungus Septoria, sprayed with broths each containing 0.2% of one of the active compounds mentioned below. After infection, the plants were placed for 2 to 3 weeks in an incubation room having a high atmospheric humidity and then checked for infestation against an untreated control series, which latter revealed a nil-return. The effects produced by the compounds of this invention are listed in the following table:

Compound No.: Effect in percent 20 93 EXAMPLE 19 Herbicidal effect in the greenhouse Preemergent Postemergent compound N o. 99 compound N0. 93

1O 9 7 0 0 10 9 7 4 0 0 10 10 10 10 1 1 8 4 2 1 2 1 10 10 8 1 10 8 10 10 10 8 6 2 10 10 10 10 4 2 10 10 4 1 7 4 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 5 1O 10 10 10 7 8 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 8 2 0 4 3 Phaseolus. 10 10 l 0 8 5 When compound No. 99 was applied in an amount of 2 kg. or over, it displayed total herbicidal properties.

When a small amount, for example 0.25 kg., of the active substance of this invention is applied, numerous test plants can be completely or almost completely destroyed without affecting, for example, soybean or phaseolus bean plants. With even smaller amounts Wild oats (Avemz fatua) in barley (Hordeum) may be controlled.

Compound No. 93, applied in an amount of 2.5 kg., was successfully applied against numerous dicotyledons and Panicum, whereas the various types of grain crops were not damaged by the active substance of the invention.

EXAMPLE 20 Test on grain crops in the field In a field of winter wheat which had just been tilled and in which the weeds had reached the 4-leaf stage, the compounds Nos. 18 and 26 were sprayed in an amount of 8.0 kg. per hectare. 3 weeks after the treatment, the effects achieved on weeds were found to be very good (that is to say value 1 and 2 respectively). Grain crops, on the other hand, had not been damaged (value 1-2).

Tests with marrow cabbage in the open The compound No. 27 was sprayed in an amount of 8.0 kg. per hectare on salad four weeks after seeding (34 leaf stage) and when the weeds had reached the stage of the large rosette.

28 The effect achieved on the weeds was good (value 3), whereas the salad was not affected by the herbicide of this invention.

Tests with marrow cabbage in the open Compound Compound No. 6 N o. 67

Amount used, kg. AS/ha 2. 0 3. 0 4. 0 3. 0 4. 0

Effect on weeds 3 3 2 2 2 Tolerance by culture plants 2 2 2 3 5 EXAMPLE 21 All compounds to be tested were formulated in the usual manner.

To check their acaricidal effect, Phaseolus plants in the 2 leaf stage were infested 12 hours before the treatment by covering them with pieces of leaves infested by a mite species (Tetranychus telarius or T etrany'chus urticae; carmine red mite). 12 hours later, the test plant was found to be covered with mites in all stages of development. The active ingredient, in the form of an emulsion, was sprayed with the aid of a fine sprayer over the plants in a manner such that a uniform layer of droplets was formed on the leaf surface. The mortality was checked 2 and 7 days later and expressed in percent. The effect upon ova cannot be stated after the test had been run for 2 days as described because the average time taken by the larvae to leave the ova has not yet been established.

At a concentration of 0.08% of active ingredient the following mortality values were found:

Compound Ova, Larvae, Adults, number percent percent percent After 7 days... 100 100 100 5 "{After 2 days 100 100 After 7 days 100 100 100 13 .{After 2 days 100 100 After 7 days 100 100 14- .{After 2 days. 100 100 After 7 days 100 100 100 15 {After 2 days. 100 100 After 7 days..- 100 29 {After 2 days 100 100 After 7 days..- 100 100 100 31 {After 2 days 100 100 After 7 days.-. 80 100 100 45 -{After 2 days 100 100 After 7 days 80 100 100 ...{After 2 days 100 100 After 7 days 100 100 100 58 {After 2 days 100 100 After 7 days 80 100 100 72 {After 2 days 100 100 After 7 days..- 80 100 100 78 ..{After 2 days 1G0 100 After 7 days... 100 it 100 91 After 2 days 100 100 Compound No. 4, applied in a concentration of 0.05%, displayed a good killing effect against red spiders, for example against Panonychus ulmi, Eotetranychus tilliae a good killing effect, in fact against both their ova and the postembryonal stages.

The following compounds show at concentrations of i i Tt 0.05% the following mortallty rate (ovicldal effect) (bum on aga nst H against Panonychus ulmi. Mortality, p rc t After 2 days After 7 days (Contr l af 7 y Cone. (p.p.m.) Larvae Adults Ova Larvae Adults Compound NO.: Mortality rate in percent igg 3g 8 3g 3g 3 95 so so 0 0 so 9 100 10 100 10 21 COMPOUND N0.156 v 56 10o 62 80 (a) Action against Teir. urttcae 78 100 Mortality, percent 3% After 2 days After 7 days 95 100 B- (D-DJIL) Larvae Adults Ova Larvae Adults 119 100 100 100 100 100 100 100 100 100 100 100 129 100 100 100 so 100 100 100 100 60 80 100 In the following tables also Tetranychus urticae which is resistent to phosphorus acid esters is listed.

. (b) Action against Tetr. telarius COMPOUND NO. 153 l Mortality, percent (a) Action against Tetr. urttcae Aft r 2 days Aft 7 days Mortality, Pemenll Cone. (p.p.m.) Larvae Adults Ova Larvae Adults After 2 y After 7 y 00 100 100 1 100 100 Gone, (p.p.m.) Larvae Adults Ova Larvae Adults 400 100 100 100 100 m0 100 100 100 100 100 2 it? 22 2a 188 O 100 100 0 80 8o COMPOUND NO.157

(a) Action against Tetr. urticae Mortality, percent (b) Action against Tetr. telariuc After 2 days After 7 days Mortality, percent Cone. (p.p.m.) Larvae Adults Ova Larvae Adults After 2 days After 7 days 100 100 60 100 100 Gone. (p.p.m.) Larvae Adults Ova Larvae 100 80 80 80 100 80 80 60 80 80 100 100 100 100 80 60 0 60 60 100 100 100 100 100 100 80 B0 100 100 0 60 (b) Action against Tart. telarius COMPOUND N0. 154 Mortality, percent (a) Action against Teir. urticae Aft 2 days After 7 days Mortality, Percent Cone. (p.p.m.) Larvae Adults Ova Larvae Adults Aftfll' 2 days After 7 days 100 0 o 80 100 Gone. (p.p.m.) Larvae Adults Ova Larvae Adults 38 38 2g g8 38 100 100 60 100 100 0 0 100 100 0 80 100 100 100 0 60 80 100 100 0 0 80 COMPOUND No.15!)

(a) Action against Tetr. urticae (b) Action against Tetr. telarius Mortality, percent Mortality, percent After 2 days After 7 days After 2 days After 7 days Cone. (p.p.m.) Larvae Adults Ova Larvae Adults Cone. (p.p.m.) Larvae Adults Ova Larvae Adults COMPOUND 155 (b) Action against Tetr. ielarius (a) Action against Tetr. urtfcae Mortality, percent Mortality, percent After 2 days After 7 days After 2 days After 7 days Conc. (p.p.m.) Larvae Adults Ova Larvae Adults Cone. (p.p.m.) Larvae Adults Ova Larvae Mortality, percent After 2 days After 7 days 00110. (p.p.m.) Larvae Adults Ova Larvae Adults (b) Action against Tetr. telariua Mortality, percent After 2 days After 7 days Cone. (p.p.m.) Larvae Adults Ova Larvae Adults EXAMPLE 22 Compound No. 4, applied in a concentration of 0.05%, displayed a good killing eifect against red spiders, for example against Panonychus ulmi, Eotetranychus tiliae in fact against both their ova and the post-embryonal stages.

Equally good results were observed with compounds Nos. 21 and 3.

EXAMPLE 23 Freshly laid ova of the flour moth Ephestia kuehniella (20 each) were placed in folded paper filters, the emulsified compound No. 36 was poured over them and they were then spread open and 'allow to dry at room temperature. When the filter had completely dried, each moth tested was covered with a wire net and kept until the untreated control moth had left its ovum. The checking of the elfects was carried out under the a binocular microscope and revealed the following total destruction (active substance in parts per million):

Concentration of active substance,

p.p.m 1,000 500 250 125 02.5 Percent killed 100 100 100 100 100 What is claimed is: 1. Oxime ethers of the formula 10 X N O:

HO CH=NO NO:

wherein X is bromine or iodine.

2. The oxime ether according to claim 1 of the formula Br N02 HO GH=N-O N02 3. The oxime ether according to claim 1 of the formula I NO:

HO- CH=NO NO:

References Cited UNITED STATES PATENTS 3,577,441 5/1971 Kaminsky et a1. 260-'566 AB 36 FOREIGN PATENTS 1,096,037 12/1967 Great Britain 260-566 AE OTHER REFERENCES Beilsteins Handbuch der Or-ganiche Chemie vol. VII, p. 895, (1968); vol. VLH, pp. 236-237 (1969).

LEON ZITVER, Primary Examiner G. A. SCHWARTZ, Assistant Examiner US. Cl. X.R.

260-247.5 R, 296 AB, 559 A, 465 E, 471 R; 7188, 94, 121; 424248, 263, 304, 324, 327

Patent No. 3,733,359

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Dated May 15 1973 In en Adolf Hubele It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 11, compound No. 37. p The partial structural formula appearing as Br Br HN I CH= should read HO Br Br Signed and sealed this 6th day of August 1971+.

(SEAL) Attest:

McCOY M. GIBSON, JR. 0. MARSHALL DANN Attesting Officer Commissioner of Patents 

